EP0691365B1 - Process for the preparation of foamed or non-foamed silicone elastomers, especially for sealing - Google Patents

Process for the preparation of foamed or non-foamed silicone elastomers, especially for sealing Download PDF

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Publication number
EP0691365B1
EP0691365B1 EP94110303A EP94110303A EP0691365B1 EP 0691365 B1 EP0691365 B1 EP 0691365B1 EP 94110303 A EP94110303 A EP 94110303A EP 94110303 A EP94110303 A EP 94110303A EP 0691365 B1 EP0691365 B1 EP 0691365B1
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Prior art keywords
component
silicone
foamed
silicone polymer
process according
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EP94110303A
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German (de)
French (fr)
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EP0691365A1 (en
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Franz Josef Giesen
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Sonderhoff Chemicals GmbH
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Sonderhoff Chemicals GmbH
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Priority to ES94110303T priority Critical patent/ES2115812T3/en
Priority to AT94110303T priority patent/ATE164862T1/en
Priority to EP94110303A priority patent/EP0691365B1/en
Priority to DE59405649T priority patent/DE59405649D1/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups

Definitions

  • the invention relates to a method for producing a foamed or non-foamed silicone elastomer with high elasticity Resilience, in particular for the manufacture of sealing elements from such a silicone elastomer, using a two-component, addition-crosslinking and platinum-catalyzed Silicone system, characterized in that a method according to claim 1 is used.
  • the object of the invention is to provide a method with which foamed or non-foamed silicone elastomers, so Silicone foams or full elastomers, or existing ones Products, such as sealing elements with high quality properties, like above all high elastic resilience good strength (compressive and tensile strength) in terms of process technology have it manufactured easily and reliably, even without it excessive annealing times.
  • high quality silicone seals such as especially sealing rings, sealing cords and the like.
  • the sealing elements also for use in areas such as. in automotive engineering, with lights or medical devices and the like should be usable in which they are exposed to special thermal stresses.
  • an organic platinum catalyst in the process mentioned at the beginning is used, based on 1000g of the reaction mass contained silicone polymer, between 300 and 3000 ppm, preferably 300 to 900 ppm, contains platinum. It is used for the SiH-containing siloxane used as crosslinker one with an SiH content of 15 mmol / g is used.
  • a two-component, addition-crosslinking Silicone system of the type mentioned provided that a special Catalysis system, preferably in combination with a special cross-linking system. While the conventional Processes platinum catalysts with a platinum content of mostly only 30 ppm per kg of silicone polymer are used, the method according to the invention works with around 10 to 100 times larger dosage of the platinum content.
  • this measure is a foamed or unexpanded silicone elastomer product with unexpected favorable properties that can be achieved primarily through extremely high elastic resilience in the order of magnitude from 95 to 100% with high mechanical strength (Compressive and tensile strength) and also improved chemical Resistance, especially oil resistance, distinguishes and at its manufacture with extremely short tempering times in the In the order of 15 to 20 min. at temperatures in the range of 120 ° to 200 ° C can be worked.
  • Results can be achieved if as a networker a powerful polyhydrogensiloxane with 15 mmol / g SiH content is used.
  • component A a foamed silicone elastomer, i.e. a product made from high quality elastic silicone foam it is advisable to use component A as water Add blowing agents, expedient in a proportion of at most 2% by weight, based on the amount of silicone polymer.
  • the two mentioned can be Components of the addition-crosslinking, platinum-catalyzed Silicone system with the help of the usual two-component mixing and dosing systems, such as those e.g. also for them
  • Polyurethane foam production can be used, the consisting of the foamed or non-foamed silicone elastomer Products, such as the sealing elements mentioned above, in situ on the components, e.g. Housing parts or housing covers u. Like., Can be produced.
  • the silicone mass Tempering heat treatment
  • cost-saving time about 15 to 20 minutes. restrict.
  • annealing can only be carried out for those according to the invention Processed silicone elastomers or products from this are carried out, their maximum operating temperature in later use above about 110 ° C lies.
  • the two components mentioned the silicone system appropriately compiled so that in a mixing ratio of 1: 1 on the two-component mixing and have the dosing system processed.
  • a non-foamed silicone elastomer (full elastomer) is made from the following Components made:
  • Component A is a compound having Component A:
  • Component B crosslinker component:
  • the two aforementioned components A and B are mixed in a mixing ratio of 1: 1 by means of a two-component mixing and metering system and onto a component, for example a valve cover, a cylinder head cover or the like. applied as a sealing bead.
  • the component is then directly in a continuous dryer over a period of 15 min. annealed at a temperature of + 150 ° C.
  • the seal produced in this way or the component provided with the seal can be installed immediately after the tempering process.
  • the values in relation to the elastic resilience of the silicone elastomer seal are 100% (according to DIN 53517).
  • the reset values of this seal in contact with the cooling water of a motor vehicle are 95 to 100%.
  • the values can be somewhat lower with aggressive media or at very high temperatures and long dwell times. Even under the most unfavorable operating conditions, the resilience of the seal is always over 65%.
  • the silicone seal produced by the aforementioned method can be used with particular advantage in motor vehicle construction and also wherever the seal is exposed to high mechanical stresses and / or thermal loads in use.
  • a foamed silicone elastomer e.g. as a seal in Automotive engineering, e.g. as a sealing cord for ignition cable covers and the like, is usable from the following components produced:
  • Component A is a compound having Component A:
  • Component B is a compound having Component B:
  • the above-mentioned components A and B are mixed using a two-component and dosing system in a mixing ratio of 1: 1 mixed and in situ as a caterpillar on the one carrying the seal Component applied.
  • the foaming process is at room temperature completed in a few minutes. Then there is a Annealing over a period of 20 min. at + 140 ° C.
  • the tempering takes place in the passage of the one carrying the seal Component through a continuous furnace.
  • the elastic resilience the seal thus obtained is at an operating temperature from 140 ° C 100% (according to DIN 53572).
  • a non-foamed silicone elastomer with an extension of about 3 days Pot life at room temperature was like manufactured as follows:
  • Component A is a compound having Component A:
  • Component B is a compound having Component B:
  • the examples given above can of course with different additives (filling, reinforcing, Thickeners and / or anti-aging agents, color pigments etc.) and also with different proportions of the additives be worked, preferably in proportions of 0 to 350g.
  • the added as a blowing agent The amount of water is 1 to 20g. That in example 1 in the Component B specified hydrogen siloxane can in an amount up to a maximum of 100 g, preferably in an amount from 40 to 80g. In example 2, this should be in component B called hydrogen siloxane in an amount of at least 100g be added. The appropriate quantity range is included here 100 to 200g.
  • the measured elastic recovery of the silicone elastomer was at an operating temperature of 150 ° C (according to DIN 53572) 0%. So there was no provision here. An elastic Rather, provision in the size range of 95% to 100% was only first given after an annealing time of 4 to 8 hours at + 150 ° C.
  • silicone foam based on the recipe according to the example 2 produced, but with the proviso that for the in the example 2 specified hydrogen siloxane one with an SiH content of 4.3 mmol / g was used. After curing was an annealing at 150 ° C for 20 min. carried out. The then determined elastic recovery of the silicone foam was about 100% at + 150 ° C (according to DIN 53572), however the pot life at room temperature increased considerably. The foam yield was also lower. This silicone foam also pointed a significantly reduced oil resistance and also poorer mechanical strength values.
  • the cheapest tempering temperature of the maximum operating temperature should match the silicone gasket for the application temperature range from 110 ° C to 200 ° C. If in Use the silicone seal a maximum operating temperature of about + 110 ° C is not exceeded, a tempering in the Usually not required. At operating temperatures above + 200 ° C is an annealing for 20 min. at an annealing temperature of + 200 ° C is sufficient. Operating temperatures above 200 ° C, e.g. of around + 240 ° C e.g. when using the silicone seals for housing seals of halogen spotlights or Halogen lights reached.
  • the siloxane can be mixed with a high SiH content
  • commercially available siloxanes are used, e.g. "Baysilone MH 15" from Bayer AG.
  • the silion material has a special high level of oil resistance.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Sealing Material Composition (AREA)

Abstract

The prodn. of foamed or unfoamed silicone elastomer with high elastic recovery (I), esp. for sealing elements, comprises reacting a two-component system consisting of (A) component (A) contg. a silicone polymer (II) with at least 2 vinyl gps./mol., an organic Pt catalyst contg. 300-3000 (pref. 300-900) ppm Pt per 1000 g silicone polymer, and opt. additives such as pyrogenic silica, pigments etc. and (B) a crosslinker component contg. poly-hydrogen-siloxane (III) and opt. other additives, in a two-component mixing and proportioning system. Pref. (III) has a SiH content of 15 mmoles/g, pref. poly-methyl-hydrogen-siloxane. Elastomer and elastomer prods. (I) are tempered for 15-20 mins. at 120-200 deg. C., pref. only in the case of prods. with a max. service temp. of more than 110 deg. C. Silicone foam (I) is made by adding water as blowing agent to component (A), pref. in an amt. of not more than 2 wt.% w.r.t. silicone polymer.

Description

Die Erfindung betrifft ein Verfahren zum Herstellen eines geschäumten oder ungeschäumten Silikonelastomers mit hohem elastischen Rückstellvermögen, insbesondere zum Herstellen von Dichtungselementen aus einem solchen Silikonelastomer, unter Verwendung eines zweikomponentigen, additionsvernetzenden und platinkatalysierten Silikonsystems, dadurch gekennzeichnet, daß ein Verfahren gemäß Anspruch 1 verwendet wird.The invention relates to a method for producing a foamed or non-foamed silicone elastomer with high elasticity Resilience, in particular for the manufacture of sealing elements from such a silicone elastomer, using a two-component, addition-crosslinking and platinum-catalyzed Silicone system, characterized in that a method according to claim 1 is used.

Verfahren der gattungsgemäßen Art sind bekannt und werden in der Praxis auch zur Herstellung von Silikondichtungen eingesetzt. Beispielsweise ist aus der EP 0 416 229 ein Verfahren zum Herstellen eines feinporigen, weichelastischen Silikon-Dichtungsschaumes für Deckel-, Gehäuse- und Hohlraumdichtungen bekannt, bei dem die Schaumstoff-Reaktionskomponenten mittels einer Niederdruck-Zweikomponenten-Misch- und Dosieranlage verarbeitet und im Freischäumungsverfahren ohne Wärmezufuhr in situ zur Aufschäumung gebracht werden, wobei die eine Reaktionskomponente ein Silikonpolymer mit mindestens zwei Vinylgruppen je Molekül, einen organischen Platinkatalysator sowie ggf. weitere Zusätze enthält, während die andere Komponente Wasserstoffsiloxan als Vernetzer enthält. Bei diesem Verfahren enthält das Reaktionsgemisch als zusätzliches Vernetzungs- und Treibmittel Wasser in einer gering dosierten Menge. Die Wasserzugabe bewirkt bei der Schäumungsreaktion einen hohen Wasserstoff-Treibeffekt.Method of the generic type Kind are known and are in practice too used for the production of silicone seals. For example is from EP 0 416 229 a method for producing a fine-pored, soft-elastic silicone sealing foam for Cover, housing and cavity seals known in which the Foam reaction components using a low-pressure two-component mixing and dosing system processed and in Free-foaming process without heat supply in situ for foaming are brought, the one reaction component Silicone polymer with at least two vinyl groups per molecule, an organic platinum catalyst and possibly other additives contains, while the other component is hydrogen siloxane as Contains crosslinker. In this process, the reaction mixture contains as an additional crosslinking and blowing agent water in a small dose. The addition of water causes the Foaming reaction has a high hydrogen blowing effect.

Die Anforderungen, die z.B. in der Automobil-, Haushaltsgeräte-, Leuchten- oder Medizinaltechnik an die Festigkeitseigenschaften und vor allem an ein gutes elastisches Rückstellvermögen (d.h. einen niedrigen Compression Set) der Dichtung gestellt werden, sind zumeist außerordentlich hoch. Es ist daher in der Vergangenheit dem Problem, Silikondichtungen zu schaffen, die diesen hohen Anforderungen genügen und sich auch unproblematisch in situ herstellen lassen, sehr viel Aufmerksamkeit gewidmet worden.The requirements, e.g. in the automotive, household appliances, Luminaire or medical technology to the strength properties and above all good elastic resilience (i.e. a low compression set) of the seal, are usually extremely high. It is therefore in the past the problem of creating silicone seals that meet high requirements and are also unproblematic have been made in situ, a lot of attention has been paid.

Verfahren, bei denen einkomponentige Silikonsysteme zum Einsatz kommen, arbeiten durchweg mit langen Reaktionszeiten, die mindestens mehrere Stunden, vielfach mehrere Tage betragen. Diese langen Reaktionszeiten erschweren und verteuern die Massenfertigung der Silikondichtungen.Processes in which one-component silicone systems are used come, work consistently with long response times, at least several hours, often several days. This Long reaction times complicate and increase the cost of mass production the silicone seals.

Bei Verwendung zweikomponentiger additionsvernetzender Silikonmassen, nämlich platinkatalysierter Vinyl/SiH-Silikonelastomere, lassen sich bei Raumtemperatur kurze Aushärtungszeiten erreichen. Das elastische Rückstellvermögen dieser Dichtungen ist allerdings für viele Einsatzzwecke ungenügend. Im Silikonelastomer zurückbleibende Wasserstoffbindungen führen beim späteren Einsatz der Dichtungen bei Druck- und/oder Wärmebelastung derselben zu einer unerwünschten Nachvernetzung und als Folge davon zu einer Herabsetzung des elastischen Rückstellvermögens der Dichtung. Es ist daher erforderlich, Silikondichtungen dieser Art nach ihrer Aushärtung einer Wärmebehandlung, d.h. einer Temperung über mehrere Stunden oder sogar mehrere Tage bei Temperaturen von 150° bis 200°C zu unterwerfen, um den Restwasserstoff abzuspalten und auf diese Weise die Nachvernetzung zu unterdrükken und ein möglichst hohes elastisches Rückstellvermögen der Dichtungen, d.h. einen niedrigen Compression Set zu erreichen. Radikalisch vernetzende Zweikomponenten-Silikonelastomere (2K-HTV) reagieren bei Raumtemperatur verhältnismäßig langsam und benötigen höhere Ausheiztemperaturen. Sie sind aufgrund der Sauerstoffinhibierung bei der Herstellung kleinerer Dichtungsmassen, wie z.B. Dichtringe oder Dichtschnüre, nicht beherrschbar und müssen im übrigen ebenfalls über längere Zeit hinweg nachgetempert werden. Längere Temperungszeiten sind aber vor allem bei der Massenherstellung von Dichtungen höchst unerwünscht.When using two-component addition-curing silicone materials, namely platinum-catalyzed vinyl / SiH silicone elastomers, short curing times can be achieved at room temperature. The elastic resilience of these seals is however, insufficient for many purposes. In the silicone elastomer remaining hydrogen bonds lead to later Use of the seals when subjected to pressure and / or heat to an undesirable post-crosslinking and as a result to reduce the elastic resilience of the Poetry. It is therefore necessary to use silicone seals this Type after curing a heat treatment, i.e. an annealing over several hours or even several days at temperatures Submit from 150 ° to 200 ° C to the residual hydrogen split off and in this way suppress the post-crosslinking and the highest possible elastic resilience Seals, i.e. to achieve a low compression set. Radically crosslinking two-component silicone elastomers (2K-HTV) react relatively slowly and at room temperature require higher baking temperatures. They are due to the oxygen inhibition in the manufacture of smaller sealants, such as. Sealing rings or sealing cords, not controllable and also have to be post-annealed for a long time will. Longer tempering times are especially important mass production of seals highly undesirable.

Aufgabe der Erfindung ist es, ein Verfahren zu schaffen, mit dem sich geschäumte oder auch ungeschäumte Silikonelastomere, also Silikonschaumstoffe oder Vollelastomere, bzw. daraus bestehende Erzeugnisse, wie vor allem Dichtelemente mit hochwertigen Eigenschaften, wie vor allem hohem elastischen Rückstellvermögen bei guter Festigkeit (Druck- und Zugfestigkeit) verfahrenstechnisch einfach und zuverlässig herstellen lassen, und zwar auch ohne übermäßig lange Temperungszeiten. Insbesondere wird mit der Erfindung die Herstellung von hochwertigen Silikondichtungen, wie vor allem Dichtringen, Dichtungsschnüren u.dgl. in situ angestrebt, wobei die Dichtelemente auch für den Einsatz in Bereichen, wie z.B. in der Kraftfahrzeugtechnik, bei Leuchten oder medizinischen Geräten u.dgl. verwendbar sein sollen, in denen sie besonderen thermischen Beanspruchungen ausgesetzt sind.The object of the invention is to provide a method with which foamed or non-foamed silicone elastomers, so Silicone foams or full elastomers, or existing ones Products, such as sealing elements with high quality properties, like above all high elastic resilience good strength (compressive and tensile strength) in terms of process technology have it manufactured easily and reliably, even without it excessive annealing times. In particular, with the invention the production of high quality silicone seals, such as especially sealing rings, sealing cords and the like. aimed in situ, the sealing elements also for use in areas such as. in automotive engineering, with lights or medical devices and the like should be usable in which they are exposed to special thermal stresses.

Die vorgenannte Aufgabe wird erfindungsgemäß dadurch gelöst, daß bei dem eingangs genannten Verfahren ein organischer Platinkatalysator verwendet wird, der, bezogen auf 1000g des in der Reaktionsmasse enthaltenen Silikonpolymers, zwischen 300 und 3000 ppm, vorzugsweise 300 bis 900 ppm, Platin enthält. Es wird dabei für das als Vernetzer verwendete SiH-haltige Siloxan ein solches mit einem SiH-Gehalt von 15 mmol/g verwendet. Nach der Erfindung wird ein zweikomponentiges, additionsvernetzendes Silikonsystem der genannten Art vorgesehen, das ein spezielles Katalysierungssystem, vorzugsweise in Kombination mit einem speziellen Vernetzersystem, aufweist. Während bei den herkömmlichen Verfahren Platinkatalysatoren mit einem Platingehalt von zumeist nur 30 ppm je kg Silikonpolymer Verwendung finden, arbeitet das erfindungsgemäße Verfahren mit einer um das 10 bis 100-fache größeren Dosierung des Platingehaltes. Überraschenderweise wurde gefunden, daß sich mit dieser Maßnahme ein geschäumtes oder ungeschäumtes Silikonelastomer-Erzeugnis mit unerwartet günstigen Eigenschaften erreichen läßt, das sich vor allem durch ein äußerst hohes elastisches Rückstellvermögen in der Größenordnung von 95 bis 100% bei zugleich hoher mechanischer Festigkeit (Druck- und Zugfestigkeit) und auch verbesserter chemischer Beständigkeit, insbesondere Ölbeständigkeit, auszeichnet und bei dessen Herstellung mit äußerst kurzen Temperungszeiten in der Größenordnung von 15 bis 20 min. bei Temperaturen im Bereich von 120° bis 200°C gearbeitet werden kann. In dieser Hinsicht optimale Ergebnisse lassen sich dabei erreichen, wenn als Vernetzer ein stark wirkendes Polyhydrogensiloxan mit 15 mmol/g SiH-Gehalt eingesetzt wird. Der Einsatz eines solchen Polyhydrogensiloxans bringt vor allem auch erhebliche Vorteile in Bezug auf die Reaktivität des Silikonsystems bei Raumtemperatur und bei der Herstellung eines geschäumten Silikonelastomers in Bezug auf die Schaumausbeute. Die durch den höheren Platingehalt sich ergebende Kostensteigerung ist im Verhältnis zu der mit der Erfindung stark verminderten Temperungs- bzw. Vernetzungszeit vernachlässigbar gering. Der Einfluß von etwaigen Inhibitoren, die die Reaktion bei Raumtemperatur in situ verlängern, z.B. eine erhöhte Vinylkonzentration (FIPFG) oder 2-Butinol (LSR) verhält sich dabei indifferent. Für das als Vernetzer verwendete Polyhydrogensiloxan, d.h. das SiH-haltige Polysiloxan, lassen sich die bekannten und handelsüblichen Wasserstoffsiloxane einsetzen, allerdings vorzugsweise solchen mit dem genannten hohen SiH-Anteil. The above object is achieved in that an organic platinum catalyst in the process mentioned at the beginning is used, based on 1000g of the reaction mass contained silicone polymer, between 300 and 3000 ppm, preferably 300 to 900 ppm, contains platinum. It is used for the SiH-containing siloxane used as crosslinker one with an SiH content of 15 mmol / g is used. According to the invention, a two-component, addition-crosslinking Silicone system of the type mentioned provided that a special Catalysis system, preferably in combination with a special cross-linking system. While the conventional Processes platinum catalysts with a platinum content of mostly only 30 ppm per kg of silicone polymer are used, the method according to the invention works with around 10 to 100 times larger dosage of the platinum content. Surprisingly it was found that this measure is a foamed or unexpanded silicone elastomer product with unexpected favorable properties that can be achieved primarily through extremely high elastic resilience in the order of magnitude from 95 to 100% with high mechanical strength (Compressive and tensile strength) and also improved chemical Resistance, especially oil resistance, distinguishes and at its manufacture with extremely short tempering times in the In the order of 15 to 20 min. at temperatures in the range of 120 ° to 200 ° C can be worked. Optimal in this regard Results can be achieved if as a networker a powerful polyhydrogensiloxane with 15 mmol / g SiH content is used. The use of such a polyhydrogen siloxane Above all, brings significant advantages in terms of Reactivity of the silicone system at room temperature and at Manufacture of a foamed silicone elastomer related to the Foam yield. The one resulting from the higher platinum content Cost increase is in relation to that with the invention greatly reduced annealing or crosslinking time is negligible low. The influence of any inhibitors that prolong the reaction in situ at room temperature e.g. a increased vinyl concentration (FIPFG) or 2-butinol (LSR) behaves indifferent. For the polyhydrogensiloxane used as crosslinker, i.e. the SiH-containing polysiloxane use the known and commercially available hydrogen siloxanes, however, preferably those with the high SiH content mentioned.

Soll ein geschäumtes Silikonelastomer, also ein Erzeugnis aus hochwertigem elastischen Silikonschaumstoff hergestellt werden, so empfiehlt es sich, der genannten Komponente A Wasser als Treibmittel zuzusetzen, zweckmäßig in einem Anteil von höchstens 2 Gew.%, bezogen auf die Menge an Silikonpolymer.Should be a foamed silicone elastomer, i.e. a product made from high quality elastic silicone foam it is advisable to use component A as water Add blowing agents, expedient in a proportion of at most 2% by weight, based on the amount of silicone polymer.

Bei dem erfindungsgemäßen Verfahren lassen sich die beiden genannten Komponenten des additionsvernetzenden, platinkatalysierten Silikonsystems mit Hilfe der gebräuchlichen Zweikomponenten-Misch- und Dosieranlagen verarbeiten, wie sie z.B. auch für die Polyurethanschaumstoffherstellung verwendet werden, wobei die aus dem geschäumten oder ungeschäumten Silikonelastomer bestehenden Erzeugnisse, wie vor allem die genannten Dichtelemente, in situ an den Bauteilen, wie z.B. Gehäuseteilen oder Gehäusedeckeln u. dgl., hergestellt werden können. Wie erwähnt, läßt sich auch die an die Aushärtung der Silikonmasse anschließende Temperung (Wärmebehandlung) auf eine betrieblich günstige und kostensparende Zeitdauer von etwa 15 bis 20 min. beschränken. Bedarfsweise kann eine Temperung nur für solche nach dem erfindungsgemäßen Verfahren hergestellte Silikonelastomere oder Erzeugnisse hieraus durchgeführt werden, deren maximale Einsatztemperatur im späteren Verwendungsfall oberhalb etwa 110°C liegt. Aus Verarbeitungsgründen werden die beiden genannten Komponenten des Silikonsystems zweckmäßig so zusammengestellt, daß sie sich im Mischungsverhältnis von 1:1 auf der Zweikomponenten-Misch- und Dosieranlage verarbeiten lassen.In the method according to the invention, the two mentioned can be Components of the addition-crosslinking, platinum-catalyzed Silicone system with the help of the usual two-component mixing and dosing systems, such as those e.g. also for them Polyurethane foam production can be used, the consisting of the foamed or non-foamed silicone elastomer Products, such as the sealing elements mentioned above, in situ on the components, e.g. Housing parts or housing covers u. Like., Can be produced. As mentioned, lets the one following the hardening of the silicone mass Tempering (heat treatment) on an operationally favorable and cost-saving time of about 15 to 20 minutes. restrict. If necessary, annealing can only be carried out for those according to the invention Processed silicone elastomers or products from this are carried out, their maximum operating temperature in later use above about 110 ° C lies. For processing reasons, the two components mentioned the silicone system appropriately compiled so that in a mixing ratio of 1: 1 on the two-component mixing and have the dosing system processed.

Weitere Merkmale der Erfindung sind in den einzelnen Ansprüchen angegeben.Further features of the invention are in the individual claims specified.

Im folgenden werden einige Beispiele für das erfindungsgemäße Verfahren angegeben.The following are some examples of the invention Procedure specified.

Beispiel 1example 1

Ein ungeschäumtes Silikonelastomer (Vollelastomer) wird aus folgenden Komponenten hergestellt: A non-foamed silicone elastomer (full elastomer) is made from the following Components made:

Komponente A:Component A:

  • 1000g Silikonpolymer mit mindestens zwei Vinylgruppen je Molekül.1000g silicone polymer with at least two vinyl groups each Molecule.
  • 3g organischer Platinkatalysator, enthaltend insgesamt 600 ppm Platin.3g organic platinum catalyst, containing a total 600 ppm platinum.
  • 100g Zusatzstoffe, wie Füll- bzw. Verstärkungsstoffe, insbesondere pyrogene Kieselsäure.100g additives, such as fillers or reinforcing materials, especially fumed silica.
  • 20g Rußpaste.20g soot paste.

    • Komponente B (Vernetzerkomponente):Component B (crosslinker component):

  • 100g Silikonpolymer mit mindestens zwei Vinylgruppen je Molekül.100g silicone polymer with at least two vinyl groups each Molecule.
  • 80g Zusatzstoffe, vorzugsweise pyrogene Kieselsäure.80g additives, preferably fumed silica.
  • 60g Wasserstoff- bzw. Polyhydrogensiloxan, z.B. Dimethylhydrogensiloxan, mit einem SiH-Gehalt von 15 mmol/g.60g hydrogen or polyhydrogen siloxane, e.g. Dimethylhydrogensiloxane, with an SiH content of 15 mmol / g.

    • Die beiden vorgenannten Komponenten A und B werden im Mischungsverhältnis 1:1 mittels einer Zweikomponenten-Misch- und Dosieranlage gemischt und auf ein Bauteil, z.B. einen Ventildeckel, einen Zylinderkopfdeckel od.dgl. als Dichtungsraupe aufgetragen. Anschließend wird das Bauteil direkt in einem Durchlauftrockner über eine Zeitdauer von 15 min. bei einer Temperatur von +150°C getempert.
    Die so hergestellte Dichtung bzw. das mit der Dichtung versehene Bauteil kann unmittelbar nach dem Temperungsvorgang verbaut werden. Die Werte in Bezug auf das elastische Rückstellvermögen der Silikonelastomerdichtung betragen 100% (nach DIN 53517). Die Rückstellwerte dieser Dichtung in Kontakt mit Kühlwasser eines Kraftfahrzeugs liegen bei 95 bis 100%. Bei Ölkontakt der Dichtung können die Werte bei agressiven Medien oder bei sehr hohen Temperaturen und langen Verweilzeiten etwas geringer sein. Auch unter ungünstigsten Einsatzbedindungen liegt das Rückstellvermögen der Dichtung stets über 65%.
    Die nach dem vorgenannten Verfahren hergestellte Silikondichtung kann mit besonderem Vorteil im Kraftfahrzeugbau und auch dort überall verwendet werden, wo die Dichtung im Einsatz hohen mechanischen Beanspruchungen und/oder thermischen Belastungen ausgesetzt ist.    The two aforementioned components A and B are mixed in a mixing ratio of 1: 1 by means of a two-component mixing and metering system and onto a component, for example a valve cover, a cylinder head cover or the like. applied as a sealing bead. The component is then directly in a continuous dryer over a period of 15 min. annealed at a temperature of + 150 ° C.
    The seal produced in this way or the component provided with the seal can be installed immediately after the tempering process. The values in relation to the elastic resilience of the silicone elastomer seal are 100% (according to DIN 53517). The reset values of this seal in contact with the cooling water of a motor vehicle are 95 to 100%. If the seal comes into contact with oil, the values can be somewhat lower with aggressive media or at very high temperatures and long dwell times. Even under the most unfavorable operating conditions, the resilience of the seal is always over 65%.
    The silicone seal produced by the aforementioned method can be used with particular advantage in motor vehicle construction and also wherever the seal is exposed to high mechanical stresses and / or thermal loads in use.

    Beispiel 2Example 2

    Ein geschäumtes Silikonelastomer, das z.B. als Dichtung im Kraftfahrzeugbau, z.B. als Dichtungsschnur bei Zündkabelabdeckungen u.dgl., verwendbar ist, wird aus folgenden Komponenten hergestellt:A foamed silicone elastomer, e.g. as a seal in Automotive engineering, e.g. as a sealing cord for ignition cable covers and the like, is usable from the following components produced:

    Komponente A:Component A:

  • 1000g Silikonpolymer mit mindestens zwei Vinylgruppen je Molekül.1000g silicone polymer with at least two vinyl groups each Molecule.
  • 6g organischer Platinkatalysator, enthaltend insgesamt 1200 ppm Platin.6g organic platinum catalyst, containing a total 1200 ppm platinum.
  • 2g Wasser (Treibmittel).2g water (blowing agent).
  • 100g pyrogene Kieselsäure.100g fumed silica.
  • 20g Rußpaste.20g soot paste.

    • Komponente B:Component B:

  • 1000g Silikonpolymer mit mindestens zwei Vinylgruppen je Molekül.1000g silicone polymer with at least two vinyl groups each Molecule.
  • 80g pyrogene Kieselsäure.80g fumed silica.
  • 120g Polyhydrogensiloxan mit einem SiH-Gehalt von120g polyhydrogensiloxane with an SiH content of
  • 15 mmol/g.15 mmol / g.

    • Die vorgenannten Komponenten A und B werden mittels einer Zweikomponenten-Misch- und Dosieranlage im Mischungsverhältnis 1:1 gemischt und in situ als Raupe auf das die Dichtung tragende Bauteil aufgetragen. Der Ausschäumungsprozeß ist bei Raumtemperatur in wenigen Minuten abgeschlossen. Es erfolgt dann eine Temperung über eine Zeitdauer von 20 min. bei +140°C. Vorzugsweise erfolgt die Temperung im Durchlauf des die Dichtung tragenden Bauteils durch einen Durchlaufofen. Das elastische Rückstellvermögen der so erhaltenen Dichtung beträgt bei einer Einsatztemperatur von 140°C 100% (nach DIN 53572).The above-mentioned components A and B are mixed using a two-component and dosing system in a mixing ratio of 1: 1 mixed and in situ as a caterpillar on the one carrying the seal Component applied. The foaming process is at room temperature completed in a few minutes. Then there is a Annealing over a period of 20 min. at + 140 ° C. Preferably the tempering takes place in the passage of the one carrying the seal Component through a continuous furnace. The elastic resilience the seal thus obtained is at an operating temperature from 140 ° C 100% (according to DIN 53572).

    Beispiel 3:Example 3:

    Die Herstellung eines ungeschäumten Silikonelastomers (Silikon-Vollelastomer) erfolgt nach Beispiel 1, jedoch mit der Maßgabe, daß dem hier angegebenen additionsvernetzenden Silikonsystem ein an sich bekannter Vinylinhibitor zugesetzt wird, welcher die Topfzeit von etwa 30 sek. auf etwa 5 min. (durch Veränderung des SiH/Vinyl-Verhältnisses) erhöht. Die Temperung erfolgt hier über eine Zeitdauer von 15 min. bei 150°C. Bei einer Einsatztemperatur von +150°C wurde eine elastische Rückstellung von 100% gemessen (nach DIN 53572).The production of a non-foamed silicone elastomer (full silicone elastomer) takes place according to example 1, but with the proviso that the addition-crosslinking silicone system specified here known vinyl inhibitor is added, which the Pot life of about 30 sec. to about 5 min. (by changing the SiH / vinyl ratio) increased. The tempering takes place here a period of 15 min. at 150 ° C. At an operating temperature an elastic recovery of 100% was measured at + 150 ° C (according to DIN 53572).

    Beispiel 4:Example 4:

    Ein ungeschäumtes Silikonelastomer mit auf etwa 3 Tage verlängerter Topfzeit bei Raumtemperatur (LSR-Qualität) wurde wie folgt hergestellt:A non-foamed silicone elastomer with an extension of about 3 days Pot life at room temperature (LSR quality) was like manufactured as follows:

    Komponente A:Component A:

    Entsprechend Beispiel 1, zusätzlich jedoch mit 3g Butinol als Inhibitor.Corresponding to example 1, but additionally with 3 g of butinol as an inhibitor.

    Komponente B:Component B:

    Gemäß Beispiel 1.According to example 1.

    Nach Aushärtung erfolgte eine Temperung bei 180°C über eine Temperungszeit von 20 min. Die elastische Rückfederung bei einer Einsatztemperatur von +180°C lag oberhalb 95% (nach DIN 53517).After curing, an annealing was carried out at 180 ° C over an annealing time from 20 min. The elastic springback in one Operating temperature of + 180 ° C was above 95% (according to DIN 53517).

    Bei den vorstehend angegebenen Beispielen kann selbstverständlich mit unterschiedlichen Zusatzstoffen (Füll-, Verstärkungs-, Verdickungs- und/oder Alterungsschutzmitteln, Farbpigmente usw.) und auch mit unterschiedlichen Mengenanteilen der Zusatzstoffe gearbeitet werden, vorzugsweise in Mengenanteilen von 0 bis 350g. Im Beispiel 2 kann die als Treibmittel zugesetzte Wassermenge bei 1 bis 20g liegen. Das im Beispiel 1 in der Komponente B angegebene Wasserstoffsiloxan kann in einer Menge bis höchstens 100g zugesetzt werden, vorzugsweise in einer Menge von 40 bis 80g. Im Beispiel 2 sollte das in der Komponente B genannte Wasserstoffsiloxan in einer Menge von mindestens 100g zugesetzt werden. Hier liegt der zweckmäßige Mengenbereich bei 100 bis 200g.The examples given above can of course with different additives (filling, reinforcing, Thickeners and / or anti-aging agents, color pigments etc.) and also with different proportions of the additives be worked, preferably in proportions of 0 to 350g. In example 2, the added as a blowing agent The amount of water is 1 to 20g. That in example 1 in the Component B specified hydrogen siloxane can in an amount up to a maximum of 100 g, preferably in an amount from 40 to 80g. In example 2, this should be in component B called hydrogen siloxane in an amount of at least 100g be added. The appropriate quantity range is included here 100 to 200g.

    Um die mit der Erfindung erzielten Vorteile deutlich zu machen, wurden die in den nachfolgenden Beispielen angegebenen Gegenversuche durchgeführt:In order to make the advantages achieved with the invention clear, were the counter-experiments given in the examples below carried out:

    Beispiel 5:Example 5:

    Es wurde ein ungeschäumtes Silikonelastomer auf der Basis der Rezeptur nach Beispiel 1 hergestellt, jedoch mit der Maßgabe, daß für den Platinkatalysator ein solcher mit einem Platin-Gehalt von 30 ppm je 1000g Silikonpolymer (anstelle von 300 ppm) eingesetzt wurde. Die Temperung erfolgte hier bei 150°C über eine Zeitdauer von 20 min.An unfoamed silicone elastomer based on the Formulation prepared according to Example 1, but with the proviso that for the platinum catalyst one with a platinum content of 30 ppm per 1000 g silicone polymer (instead of 300 ppm) was used. The tempering took place here at 150 ° C a period of 20 min.

    Die gemessene elastische Rückstellung des Silikonelastomers betrug bei einer Einsatztemperatur von 150°C (nach DIN 53572) 0%. Es war hier also keine Rückstellung gegeben. Eine elastische Rückstellung im Größenbereich von 95% bis 100% war vielmehr erst nach einer Temperungszeit von 4 bis 8 Stunden bei +150°C gegeben.The measured elastic recovery of the silicone elastomer was at an operating temperature of 150 ° C (according to DIN 53572) 0%. So there was no provision here. An elastic Rather, provision in the size range of 95% to 100% was only first given after an annealing time of 4 to 8 hours at + 150 ° C.

    Beispiel 6:Example 6:

    Es wurde ein Silikonschaum auf der Basis der Rezeptur nach Beispiel 2 hergestellt, jedoch mit der Maßgabe, daß für das im Beispiel 2 angegebene Wasserstoffsiloxan ein solches mit einem SiH-Gehalt von 4,3 mmol/g eingesetzt wurde. Nach der Aushärtung wurde eine Temperung bei 150°C über 20 min. durchgeführt. Die anschließend bestimmte elastische Rückfederung des Silikonschaums betrug zwar etwa 100% bei +150°C (nach DIN 53572), jedoch verlängerte sich die Topfzeit bei Raumtemperatur erheblich. Auch war die Schaumausbeute geringer. Außerdem wies dieser Silikonschaum eine deutlich verminderte Ölbeständigkeit und auch schlechtere mechanische Festigkeitswerte auf.There was a silicone foam based on the recipe according to the example 2 produced, but with the proviso that for the in the example 2 specified hydrogen siloxane one with an SiH content of 4.3 mmol / g was used. After curing was an annealing at 150 ° C for 20 min. carried out. The then determined elastic recovery of the silicone foam was about 100% at + 150 ° C (according to DIN 53572), however the pot life at room temperature increased considerably. The foam yield was also lower. This silicone foam also pointed a significantly reduced oil resistance and also poorer mechanical strength values.

    Aus den Versuchsergebnissen wurde das in der Zeichnung dargestellte Diagramm erstellt, das die Abhängigkeit des elastischen Rückstellvermögens der nach den Beispielen 1 und 2 hergestellten Silikonelastomere in Abhängigkeit von der Temperungs- bzw. Wärmebehandlungszeit t bei einer durchschnittlichen Temperungstemperatur von +150°C zeigt. Aus dem Verlauf der Kurve X ist erkennbar, daß bei den Rezepturen nach den Beispielen 1 und 2 das optimale Rückstellvermögen bei einer Temperungszeit zwischen 10 und 15 min. erreicht wird, wobei dieser Zeitwert in einer gewissen Abhängigkeit von der Masse des der Temperung unterworfenen Silikonelastomers und auch von der Art der Ofenanlage steht. Temperungszeiten oberhalb 20 min. bringen bezüglich des Rückstellvermögens keine Verbesserungen.From the test results that was shown in the drawing Diagram created that shows the dependence of elastic Resilience of those produced according to Examples 1 and 2 Silicone elastomers depending on the annealing or heat treatment time t at an average annealing temperature of + 150 ° C shows. From the course of curve X it can be seen that in the recipes according to Examples 1 and 2 that optimal resilience with a tempering time between 10 and 15 min. is reached, this time value in a certain Dependence on the mass of the one subjected to the annealing Silicone elastomers and also from the type of furnace system. Annealing times above 20 min. bring in terms of resilience no improvements.

    Ferner konnte festgestellt werden, daß bei Temperungszeiten von 20 min. die günstigste Temperungstemperatur der maximalen Einsatztemperatur der Silikondichtung entsprechen sollte, und zwar für den Einsatz-Temperaturbereich von 110°C bis 200°C. Wenn im Einsatz der Silikondichtung eine maximale Einsatztemperatur von etwa +110°C nicht überschritten wird, ist eine Temperung in der Regel nicht erforderlich. Bei Einsatztemperaturen oberhalb +200°C ist eine Temperung über 20 min. bei einer Temperungstemperatur von +200°C ausreichend. Einsatztemperaturen oberhalb 200°C, z.B. von etwa +240°C werden z.B. bei Verwendung der Silikondichtungen für Gehäuseabdichtungen von Halogenstrahlern bzw. Halogenleuchten erreicht.It was also found that at tempering times of 20 min. the cheapest tempering temperature of the maximum operating temperature should match the silicone gasket for the application temperature range from 110 ° C to 200 ° C. If in Use the silicone seal a maximum operating temperature of about + 110 ° C is not exceeded, a tempering in the Usually not required. At operating temperatures above + 200 ° C is an annealing for 20 min. at an annealing temperature of + 200 ° C is sufficient. Operating temperatures above 200 ° C, e.g. of around + 240 ° C e.g. when using the silicone seals for housing seals of halogen spotlights or Halogen lights reached.

    Insgesamt ergibt sich, daß mit dem erfindungsgemäß vorgeschlagenen Katalysatorsystem mit hohem Platingehalt in Verbindung mit einem stark wirkenden Polyhydrogensiloxan die Temperungszeiten überraschend stark verkürzt werden können und dabei außerordentlich hochwertiges Silikonelastomer bzw. Silikonelastomer-Erzeugnisse erhalten werden, die den vor allem bei Dichtungen gestellten hohen Anforderungen voll genügen.Overall, it follows that with the proposed according to the invention High platinum catalyst system in conjunction with a strongly acting polyhydrogensiloxane the tempering times can be shortened surprisingly strongly and thereby extraordinarily high quality silicone elastomer or silicone elastomer products can be obtained, which is mainly provided for seals meet high requirements.

    Bei dem erfindungsgemäßen Verfahren können für das Siloxan mit einem hohen SiH-Gehalt handelsübliche Siloxane verwendet werden, z.B. "Baysilone MH 15" der Firma Bayer AG.In the process according to the invention, the siloxane can be mixed with a high SiH content, commercially available siloxanes are used, e.g. "Baysilone MH 15" from Bayer AG.

    Die gute Mineralölbeständigkeit des nach dem erfindungsgemäßen Verfahren hergestellten Silikonelastomers ergibt sich aus der nachfolgenden Tabelle, die sich auf das nach Beispiel 1 hergestellte Silikonelastomer bezieht, wobei in der Spalte "Ausgangszustand" die Ursprungseigenschaften des Silikonelastomers und unter der Spalte "nach Lagerung" die Eigenschaften dieses Silikonelastomers nach einer Lagerung über eine Zeitdauer von 7 Tagen bei 100°C in Öl (ASTM-Öl Nr. 2) angegeben sind: Eigenschaften Nach Lagerung Ausgangszustand Shore A 65 68 Volumenänderung + 8 % - Reißfestigkeit 7,0 N/mm2 7,5 N/mm2 Reißdehnung 104 % 102% The good mineral oil resistance of the silicone elastomer produced by the process according to the invention can be seen from the table below, which relates to the silicone elastomer produced according to Example 1, the original properties of the silicone elastomer in the "Initial state" column and the properties of the silicone elastomer under the "After storage" column Silicone elastomers after storage for 7 days at 100 ° C in oil (ASTM oil No. 2) are given: characteristics After storage Initial state Shore A 65 68 Volume change + 8% - Tensile strength 7.0 N / mm 2 7.5 N / mm 2 Elongation at break 104% 102%

    Wie die Tabelle ausweist, weist das Silionmaterial ein besonders hohes Niveau an Ölbeständigkeit auf.As the table shows, the silion material has a special high level of oil resistance.

    Claims (8)

    1. A process for producing a foamed or non-foamed silicone elastomer having a high elastic restoring capacity, using a two-component, addition-crosslinking and platinum-catalysed silicone system, wherein component (A), containing
         a silicone polymer comprising at least 2 vinyl groups per molecule, an organic platinum catalyst, and optionally other additives also,
      is processed with crosslinking component (B), containing
         polyhydrogen siloxane and optionally other additives also,
      by means of a two-component mixing and proportioning unit and is reacted in situ, characterised by the combination of the following features:
      an organic platinum catalyst is used which contains between 300 and 3000 ppm platinum with respect to 1000 g of the silicone polymer contained in the reaction mass;
      a polyhydrogen siloxane with an SiH content of 15 mmoles/g is used as the polyhydrogen siloxane;
      the silicone elastomer or the product produced therefrom is subjected to an annealing operation at a temperature of 120°C to 200°C for a period of 15 to 20 minutes.
    2. A process according to claim 1, characterised in that dimethyl hydrogen siloxane is used as the polyhydrogen siloxane.
    3. A process according to claim 1 or 2, characterised in that in order to produce a foamed silicone elastomer water is added to component (A) as a foaming agent, in an amount of 2 % by weight at most with respect to the amount of silicone polymer.
    4. A process according to any one of claims 1 to 3, characterised in that a vinyl inhibitor is added to the addition-crosslinking silicone system in order to adjust the pot life at room temperature.
    5. A process according to any one of claims 1 to 4, characterised in that components (A) and (B) are processed in a mixture ratio of 1 : 1 in the two-component mixing and proportioning unit, wherein each of the two components contains a silicone polymer comprising at least two vinyl groups per molecule, and optionally other additives also.
    6. A process according to any one of claims 1 to 5, characterised in that a non-foamed silicone polymer product is produced from component (A), containing
      1000 g silicone polymer comprising at least two vinyl groups per molecule, an organic platinum catalyst, containing a total of 600 ppm platinum,
      0 to 300 g fillers or reinforcing agents,
      0 to 20 g carbon black paste,
      and crosslinking component (B), containing
      1000 g silicone polymer comprising at least two vinyl groups per molecule,
      40 to 80 g polyhydrogen siloxane with an SiH content of 15 mmoles/g,
      0 to 300 g additive substances,
      wherein components (A) and (B) are mixed by means of a two-component mixing and proportioning unit and are applied, e.g. in the form of a bead, to a component, and the component is subsequently subjected to an annealing operation.
    7. A process according to any one of claims 1 to 5, characterised in that a foamed silicone elastomer is produced from component (A), containing
      1000 g silicone polymer comprising at least two vinyl groups per molecule,
      6 g organic platinum catalyst containing a total of at least 1200 ppm platinum,
      1 to 20 g water (foaming agent),
      0 to 300 g additive substances,
      wherein components (A) and (B) are processed by means of a two-component mixing and proportioning unit and are applied, e.g. as a housing or cover seal, to a component and are foamed in situ, whereupon an annealing operation is performed.
    8. Application of the process according to one or more of claims I to 7 to the production of thermally stressed seals, such as primarily cover or housing seals.
    EP94110303A 1994-07-02 1994-07-02 Process for the preparation of foamed or non-foamed silicone elastomers, especially for sealing Expired - Lifetime EP0691365B1 (en)

    Priority Applications (4)

    Application Number Priority Date Filing Date Title
    ES94110303T ES2115812T3 (en) 1994-07-02 1994-07-02 PREPARATION PROCEDURE FOR SILICONE ELASTOMER, FOAMY OR NON-FOAMY, IN PARTICULAR FOR SEALING.
    AT94110303T ATE164862T1 (en) 1994-07-02 1994-07-02 METHOD FOR PRODUCING A FOAMED OR UNFOAMED SILICONE ELASTOMER, PARTICULARLY FOR SEALING PURPOSES
    EP94110303A EP0691365B1 (en) 1994-07-02 1994-07-02 Process for the preparation of foamed or non-foamed silicone elastomers, especially for sealing
    DE59405649T DE59405649D1 (en) 1994-07-02 1994-07-02 Process for producing a foamed or non-foamed silicone elastomer, in particular for sealing purposes

    Applications Claiming Priority (1)

    Application Number Priority Date Filing Date Title
    EP94110303A EP0691365B1 (en) 1994-07-02 1994-07-02 Process for the preparation of foamed or non-foamed silicone elastomers, especially for sealing

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    EP0691365A1 EP0691365A1 (en) 1996-01-10
    EP0691365B1 true EP0691365B1 (en) 1998-04-08

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    AT (1) ATE164862T1 (en)
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    Cited By (4)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US6022904A (en) * 1998-02-26 2000-02-08 Wacker--Chemie RTV-2 silicone foams with low compression set
    DE102008011986A1 (en) 2008-02-29 2009-09-10 Sonderhoff Chemicals Gmbh Condensation-crosslinking silicone foams
    WO2017093959A1 (en) 2015-12-03 2017-06-08 Sonderhoff Chemichals Gmbh Photoactivatable multi-component systems for producing a foamed silicone composition
    CN110437620A (en) * 2019-08-23 2019-11-12 深圳市红叶杰科技有限公司 A kind of foamed silica gel and preparation method thereof for making foaming agent using water

    Families Citing this family (3)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE102004010755A1 (en) * 2004-03-05 2005-09-22 Degussa Ag silicone rubber
    EP4100465A1 (en) * 2020-02-05 2022-12-14 Dow Global Technologies LLC The preparation of foamed silicone elastomers
    EP4384569A1 (en) * 2021-08-11 2024-06-19 Dow Global Technologies LLC The preparation of foamed silicone products

    Family Cites Families (2)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US5169727A (en) * 1988-08-04 1992-12-08 Minnesota Mining And Manufacturing Company Silicone-based pressure-sensitive adhesives having high solids content
    US4916169A (en) * 1988-09-09 1990-04-10 Minnesota Mining And Manufacturing Company Visible radiation activated hydrosilation reaction

    Cited By (5)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US6022904A (en) * 1998-02-26 2000-02-08 Wacker--Chemie RTV-2 silicone foams with low compression set
    DE102008011986A1 (en) 2008-02-29 2009-09-10 Sonderhoff Chemicals Gmbh Condensation-crosslinking silicone foams
    WO2017093959A1 (en) 2015-12-03 2017-06-08 Sonderhoff Chemichals Gmbh Photoactivatable multi-component systems for producing a foamed silicone composition
    DE102015121053A1 (en) 2015-12-03 2017-06-08 Sonderhoff Chemicals Gmbh Photoactivatable multicomponent systems for producing a foamed silicone composition
    CN110437620A (en) * 2019-08-23 2019-11-12 深圳市红叶杰科技有限公司 A kind of foamed silica gel and preparation method thereof for making foaming agent using water

    Also Published As

    Publication number Publication date
    DE59405649D1 (en) 1998-05-14
    ATE164862T1 (en) 1998-04-15
    EP0691365A1 (en) 1996-01-10
    ES2115812T3 (en) 1998-07-01

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